CN103627430A - Hydrogenation method used for direct production of low-condensation point lubricant base oil - Google Patents
Hydrogenation method used for direct production of low-condensation point lubricant base oil Download PDFInfo
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Abstract
The invention discloses a hydrogenation method used for direct production of low-condensation point lubricant base oil. The hydrogenation method comprises following methods, raw oil and hydrogen are mixed, and an obtained mixture is delivered into a hydrogenation refining reactor and a hydrocracking reactor successively, and is contacted with a hydrocracking catalyst for reaction; H2S of a reaction effluent of the hydrocracking reactor is removed using a high-pressure stripping tower, and then the reaction effluent is delivered into a post-refining reactor, and is contacted with a precious metal post-hydrogenation refining catalyst for reaction, wherein reaction temperature of the post-refining reactor is 50 to 200 DEG C lower than that of the hydrocracking reactor; and hydrogen-rich gas, naphtha cut fractions, middle fraction oil and tail oil cur fractions are obtained via separation and fractionation of a post-refining reactor effluent. According to the hydrogenation method, the lubricant base oil with low condensation point, high viscosity indexes and excellent oxidation stability can be obtained directly via the hydrogenation method; in addition, combined production of high-quality diesel oil and light products, such as naphtha and aviation kerosene, can be realized.
Description
Technical field
The invention belongs to a kind of method for hydrogen cracking that obtains low boiler cut hydrocarbon ils in the situation that there is hydrogen, more particularly, is for directly increasing production the method for hydrogen cracking of low freezing point diesel fuel and lubricant base.
Background technology
Increasingly strict along with environmental requirement in the variation year by year of crude quality and world wide, hydrocracking process as one of Main Means of crude oil secondary processing, heavy oil lighting, because adaptability to raw materials is strong, production decision is flexible, liquid product yield is high, good product quality is being brought into play more and more important effect in sulfur-bearing and high-sulfur crude oil deep processing production clean fuel process, and its range of application is also increasingly extensive.
In recent years, environmental regulation has proposed more and more higher requirement to the performance of lubricant base, the tail oil that existing hydrocracking technology obtains has higher viscosity index conventionally, but condensation point is higher, oxidation stability is poor, need could obtain qualified lubricant base after follow-up pour point depression technique and post-refining process process, pour point depression technique can adopt solvent dewaxing or isomerization dewaxing, and post-refining can adopt solvent treatment or hydrofinishing.
CN1183493C discloses the method for hydrogen cracking of a kind of Low Freezing Point diesel oil and ethylene raw processed.The method adopts the classification filling scheme of Y molecular sieve and two kinds of hydrocracking catalysts of beta-molecular sieve, can further improve intermediate oil yield, significantly reduce the condensation point of diesel product, obtain the tail oil that BMCI value is lower simultaneously, but in the method, tail oil is the raw material as preparing ethylene by steam cracking, its condensation point is higher, needs further pour point depression to process during for the production of lubricant base.
CN1107710C discloses hydrocracking catalyst of a kind of intermediate oil and preparation method thereof, the feature of described catalyzer is to contain a kind of efficient synthetic modified beta molecular sieve as acidic cleavage component, can further improve the selectivity of middle runnings, be applicable to inceasing output of jet fuel and clean diesel, the crack characteristic of beta-molecular sieve contributes to Low Freezing Point diesel oil simultaneously.But and the production of not mentioned lubricant base.
Summary of the invention
Object of the present invention provides the method for hydrogen cracking of a kind of direct production low freezing point diesel fuel and lubricant base on prior art basis, to overcome in prior art, hydrocracking tail oil needs follow-up independent pour point depression technique and post-refining process process just can obtain the problem of qualified lubricant base.
Method provided by the invention comprises: after (1) stock oil mixes with hydrogen, enters hydrofining reactor, contacts and react with Hydrobon catalyst,
(2) reaction effluent of hydrofining reactor enters hydrocracking reactor, and contact and react with hydrocracking catalyst,
(3) reaction effluent of hydrocracking reactor removes H through high-pressure stripper
2after S, enter rear refining reaction device, contact and react with back end hydrogenation catalyst for refining, described back end hydrogenation catalyst for refining is the loaded catalyst that contains precious metal, and the temperature of reaction of rear refining reaction device is lower 50～200 ℃ than the temperature of reaction of hydrocracking reactor,
(4) after, refining reaction device effluent, after separated and fractionation, obtains hydrogen-rich gas, naphtha fraction, intermediate oil and tail oil cut.
The boiling range scope of stock oil of the present invention is 300-650 ℃.Preferably do for oneself from the straight run vacuum gas oil (VGO) of water distilling apparatus and/or from the wax tailings (CGO) of coker, sulphur content is not more than 50000 μ g/g, preferably be not more than 40000 μ g/g, nitrogen content is not more than 5000 μ g/g and is preferably not more than 3000 μ g/g.
In described product, the cut point of diesel oil distillate and tail oil cut is 350～390 ℃.
Under the condition that fresh feed oil exists at hydrogen, enter hydrofining reactor, contact reactions such as carrying out hydrogenating desulfurization, hydrodenitrification, a small amount of aromatic saturation with Hydrobon catalyst, the reaction conditions of hydrofining reactor is: 300～450 ℃ of temperature of reaction, reaction pressure 3.0～20.0MPa, hydrogen to oil volume ratio 300～2000, volume space velocity is 0.1～5.0h
-1.
The reaction effluent of hydrofining reactor directly enters hydrocracking reactor, contact with hydrocracking catalyst and carry out hydrocracking reaction, the reaction conditions of hydrocracking reactor is: temperature of reaction is 300～450 ℃, reaction pressure 3.0～25.0MPa, hydrogen to oil volume ratio 300～2000, volume space velocity is 0.5～8.0h
-1.
The reaction effluent of hydrocracking reactor removes H through high-pressure stripper
2s, described high pressure gas stripper adopts hydrogen air lift, and the operational condition of high pressure gas stripper is 5.0～15.0MPa.The gaseous stream of high pressure gas stripper gained enters circulating hydrogen compressor, after the liquid phase stream of high pressure gas stripper gained mixes with fresh hydrogen, enters rear refining reaction device.
In rear refining reaction device, remove H
2the reaction product of the hydrocracking reactor of S contacts and carries out rear refining reaction with precious metal back end hydrogenation catalyst for refining, to improve the oxidation stability of tail oil.The reaction conditions of rear refining reaction device is: temperature of reaction is 120～300 ℃, and reaction pressure is 3.0～25.0MPa, hydrogen to oil volume ratio 300～2000, and volume space velocity is 0.3～8.0h
-1.This reactor operates under lower temperature of reaction, and the degree of depth of favourable a small amount of unsaturated hydrocarbons is saturated.
Described Hydrobon catalyst is to load on amorphous alumina or/and the loaded catalyst of the group vib base metal on sial or VIII family base metal or its combination.Preferred Hydrobon catalyst is with γ-Al
2o
3for carrier, catalyst activity component is one or more in Mo, W, Co, the Ni of group vib and VIII family metal component in the periodic table of elements.
Described precious metal back end hydrogenation catalyst for refining is loaded catalyst, carrier is heat-resistant inorganic oxide, load hydrogenation activity component, described hydrogenation activity component concentration, in oxide compound, be 0.01～15 heavy %, be selected from least one platinum, palladium precious metal or itself and the group that formed by molybdenum, nickel, vanadium, cobalt, tungsten in the mixture of one or more metals.Preferred hydrogenation activity component is a kind of combination in nickel-platinum, nickel-palladium, nickel-platinum-palladium, platinum-palladium.
When described hydrogenation active metals component is selected from the nickel, platinum of group VIII and/or metallic palladium component, in metal and take catalyzer as benchmark, the content of described group VIII metal is preferably 0.1～7 % by weight, more preferably 0.1～5 % by weight.While containing platinum and palladium in described hydrogenation active metals component, Pd/(Pt+Pd wherein) weight ratio is 0.3～1.0, preferably 0.5～0.8.
The optional self-alumina of described carrier, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, aluminum oxide-magnesium oxide, silicon oxide-magnesium oxide, silicon oxide-zirconium white, silicon oxide-Thorotrast, silicon oxide-beryllium oxide, silicon oxide-titanium oxide, silicon oxide-zirconium white, oxidation titania-zirconia, silica-alumina-Thorotrast, silica-alumina-titanium oxide, silica-alumina-magnesium oxide, silica-alumina-zirconium white, natural zeolite, one or more in clay.Preferred aluminum oxide and/or silica-alumina wherein.
Described precious metal back end hydrogenation catalyst for refining can also contain selectable adjuvant component, is one or more in boron, fluorine, chlorine and phosphorus, take catalyzer as benchmark, and the content of adjuvant component is 0.1%～5.0 % by weight.
Described hydrocracking catalyst contains complex carrier and loads on group vib metal and the group VIII metal on this complex carrier, in oxide compound, the total amount of this catalyzer of take is benchmark, the content of described group vib metal is 15～35 % by weight, the content of described group VIII metal is 2～8 % by weight, the content of described complex carrier is 57～86 % by weight, and wherein complex carrier is comprised of molecular sieve and amorphous composite oxides.
In preferred described complex carrier, molecular sieve is beta-molecular sieve, and described amorphous composite oxides are silicon oxide, aluminum oxide, titanium oxide, zirconium white is independent or their arbitrary combination.More preferably described complex carrier is comprised of aluminum oxide, silica-alumina and beta-molecular sieve, take complex carrier as benchmark, aluminum oxide 25～80 % by weight, silica-alumina 15～70 % by weight, beta-molecular sieve 0.5～15 % by weight.
The most probable aperture of the complex carrier of described hydrocracking catalyst is 3～20nm, the aperture concentration degree of carrier is 15～42, described most probable aperture is to adopt BET method to measure, described aperture concentration degree refers to and adopts in dV/dr that BET method the measures distribution curve with varying aperture, the ratio of the height at peak and the halfwidth at this peak, dV/dr represents the long-pending differential to aperture of specific pore volume.The most probable aperture of the complex carrier of preferred described hydrocracking catalyst is 5～15nm, and the aperture concentration degree of carrier is 18～40.
In the present invention, term " most probable aperture " refers to: when adopting the pore structure of BET method measure sample, the specific pore volume of acquisition long-pending to the differential in aperture (that is, and dV/dr) in the distribution curve with aperture, the corresponding aperture of maximum value of dV/dr.Adopt BET method to measure the pore structure of porous mass, to obtain specific pore volume long-pending, to the differential in aperture, with the method for the distribution curve in aperture, be known in those skilled in the art, for example can be according to < < Petrochemical Engineering Analysis method > > (Science Press, nineteen ninety first version, the volumes such as Yang Cuiding) in the method stipulated in the RIPP 151-90 that records measure.
In the present invention, term " aperture concentration degree " refers to: when adopting the pore structure of BET method measure sample, the specific pore volume of acquisition amasss the differential in aperture in the distribution curve with aperture, the ratio of the halfwidth at peak height and this peak.The ratio of the halfwidth at peak height and this peak is larger, shows that the aperture intensity of porous support is higher.
According to the present invention, while there is a plurality of peak in the distribution curve at described dV/dr with varying aperture, the ratio of the peak height at each peak and the halfwidth at this peak all should meet above-mentioned requirements.
Fig. 1 is that the specific pore volume of the porous support of the embodiment of the present invention 1 preparation amasss to the differential in aperture the distribution curve schematic diagram with aperture.In Fig. 1, X-coordinate is the aperture of porous support, adopts logarithmic coordinates, and unit is
ordinate zou is the long-pending differential to aperture of specific pore volume.In Fig. 1, M represents peak height (that is, maximum dV/dr), and N represents that (that is,, on described distribution curve, ordinate zou is halfwidth
distance between two points of M).When calculated hole diameters concentration degree, halfwidth and peak height all adopt the unit of length.
The complex carrier of hydrocracking catalyst of the present invention is prepared by the following method: the precursor of amorphous composite oxides, beta molecular sieve, peptizing agent and water are mixed, to supply raw materials; Described raw material is sent in forcing machine, and after kneading, extruded in forcing machine, to obtain formed body; Described formed body is carried out to roasting, and to obtain described complex carrier, wherein, the temperature of described formed body in the exit of described forcing machine is 40～150 ℃.
In prior art, with forcing machine, raw material is being extruded, to obtain in the process of formed body, the temperature of generally cooling conditions of described forcing machine being controlled to the formed body for making to extrude is room temperature left and right (lower than 40 ℃).But the present invention controls and to make the temperature of formed body in the exit of described forcing machine is 40～150 ℃, can make most probable aperture and the aperture concentration degree of the carrier prepared by this formed body meet previously described requirement.Preferably, the temperature of described formed body in the exit of described forcing machine is 60～98 ℃.
The present invention is not particularly limited for the kind of the precursor of described amorphous composite oxides.Usually, described precursor can be: the hydrous oxide of described amorphous composite oxides, the gel of precursor that contains amorphous composite oxides and the colloidal sol of the precursor that contains amorphous composite oxides.In the present invention, term " hydrous oxide " refers to the hydrate of oxide compound.
For example, when described amorphous composite oxides are aluminum oxide, the example of described precursor can include but not limited to: hydrated aluminum oxide (for example: aluminium hydroxide, pseudo-boehmite), the gel that contains hydrated aluminum oxide and the colloidal sol that contains hydrated aluminum oxide.
When the average particulate diameter of the precursor of described amorphous composite oxides is 40～100nm, the carrier of preparation has higher aperture concentration degree.The angle of the aperture concentration degree of the carrier of preparing from further raising, the average particulate diameter of the precursor of described amorphous composite oxides is preferably 40～80nm, more preferably 40～60nm.
In the present invention, described average particulate diameter is to adopt XRD method, by the Scherrer formula shown in formula I, calculated,
In formula I, D is average particulate diameter;
λ is the wavelength of X ray;
β HKL is the broadening degree that the high peak intensity of diffracted ray half place causes because of grain fineness number refinement, wherein, and β HKL=B-B0;
B is the peak width at half height of actual measurement;
B0 is the broadening degree of instrument;
θ is input angle.
In amorphous composite oxides precursor, containing relative crystallinity is more than 80% pseudo-boehmite.In amorphous composite oxides precursor of the present invention, preferably contain the pseudo-boehmite that can form aluminum oxide under roasting condition.Although adopt various pseudo-boehmites all can form aluminum oxide, adopting relative crystallinity is that more than 80% pseudo-boehmite can guarantee that final carrier has under the condition of large aperture and pore volume, further improves the aperture concentration degree of the carrier obtaining.The relative crystallinity of described pseudo-boehmite is preferably more than 90%, and more preferably 90～110%.
In the present invention, described relative crystallinity, to adopt < < Petrochemical Engineering Analysis method > > (Science Press, nineteen ninety first version, Yang Cui is the volume such as surely) in the method stipulated in the RIPP 139-90 that records measure, wherein, the standard specimen using is the sample that is numbered S87-16B, the absolute crystallinity of this standard specimen is 98.0%, can be commercially available by Research Inst. of Petroleum Processing, SINOPEC.
The active metal component of described hydrocracking catalyst is molybdenum, tungsten, nickel, cobalt or its combination.
In described hydrocracking catalyst, also contain phosphorus, fluorine, boron, basic metal or alkaline-earth metal, or its combination.
The preparation method of hydrocracking catalyst of the present invention comprises: the hydrogenation activity composition with katalysis is loaded on complex carrier, can contact with described complex carrier for the aqueous solution of the compound that contains hydrogenation activity component, dry and roasting.
The present invention is not particularly limited the temperature of described dipping, can be all temps that steeping fluid can reach.Time to dipping is not particularly limited, and for example, the temperature of dipping can be 5-150 ℃, and dipping time can be 0.5-12 hour.
Described dry temperature can be 100-300 ℃, is preferably 105-250 ℃; The dry time can be 1-24 hour, is preferably 2-12 hour.
The temperature of roasting can be 350-600 ℃, is preferably 400-550 ℃; The time of roasting can be 1-10 hour, is preferably 2-8 hour.
Hydrocracking catalyst of the present invention has moderate pore passage structure, wherein can several holes larger, is conducive to the diffusion of the heavy ends that molecular dimension is larger, is also conducive to intermediate oil and optionally improves, in addition, owing to determining that the principal element of petroleum products questionable points is the content of paraffinic hydrocarbons in product (especially straight-chain paraffin), therefore the present invention is according to the reaction characteristics of heavy crude hydro carbons hydrocracking, make hydrocracking catalyst there is kind and the number of suitable acidic components, the matched well state of acidic components and hydrogenation component, and the suitable pore size and distribution of carrier, thereby effectively improve the selectivity of paraffinic hydrocarbons reaction, realize the dealkylation of macromole aromatic hydrocarbons, can reduce to greatest extent the paraffinicity in tail oil, increase naphthenic hydrocarbon and isoparaffin content.
Adopt method provided by the invention, by a kind of technological process, can directly obtain low condensation point, high viscosity index (HVI), lubricant base that oxidation stability is good, and saved required pour point depression technological process and the post-refining process process of traditional lubrication oil base plinth oil production process, greatly saved plant investment and process cost.Meanwhile, adopt present method, the light-end productss such as fine-quality diesel oil that can the low condensation point of coproduction and petroleum naphtha, boat coal.
Accompanying drawing explanation
Fig. 1 is that the specific pore volume of the complex carrier of the embodiment of the present invention 1 preparation amasss to the differential in aperture the distribution curve schematic diagram with aperture.
Fig. 2 is the schematic flow sheet of the method for hydrotreating of direct production lubricant base provided by the present invention.
Embodiment
Below by accompanying drawing, method provided by the invention is illustrated further, but not thereby limiting the invention.
As shown in Figure 2, from the stock oil of pipeline 11 and new hydrogen from pipeline 12, make-up hydrogen compressor 1, mix by pipeline 13 and enter process furnace 2, mixture after heating enters hydrofining reactor 3 through pipeline 14, under the effect of Hydrobon catalyst, there is desulfurization, denitrogenation and a small amount of aromatic saturation reaction, after reaction, logistics directly enters hydrocracking reactor 4 through pipeline 18, under the effect of hydrocracking catalyst, carry out the reactions such as de-alkyl of cracking, macromole aromatic hydrocarbons.The reaction effluent of hydrocracking reactor enters high pressure gas stripper 5 through pipeline 19 and pipeline 20, from the new hydrogen of make-up hydrogen compressor 1, pipeline 15, pipeline 16 as air lift medium, the gaseous stream obtaining after air lift is delivered to circulating hydrogen compressor 8 through pipeline 21, liquid phase stream after air lift is with after new hydrogen from make-up hydrogen compressor 1, pipeline 15, pipeline 17 mixes, refining reaction device 6 after pipeline 22 enters, under the effect of precious metal back end hydrogenation catalyst for refining, carry out rear refining reaction.
The reaction effluent of rear refining reaction device 6 enters high-pressure separator 7 through pipeline 23 and carries out gas-liquid separation, the hydrogen-rich gas at high-pressure separator top enters circulating hydrogen compressor 8 through pipeline 24, through circulating hydrogen compressor supercharging, by pipeline 27, returns to hydrofining reactor and hydrocracking reactor.High-pressure separator bottom is discharged sour water and is discharged through pipeline 26, high-pressure separator 6 bottom liquid phase streams enter light pressure separator 9 through pipeline 25, at this, carry out further gas-liquid separation, the gas that separation obtains is discharged through pipeline 28, the sour water that separation obtains is discharged through pipeline 30, and the liquid of light pressure separator 9 bottoms enters separation column 10 through pipeline 29 and carries out fractionation.Separation column 10 tower tops separate lighter hydrocarbons and naphtha fraction is extracted out through pipeline 31, and kerosene(oil)fraction is extracted out through pipeline 32, and diesel oil distillate is extracted out through pipeline 33, and the tail oil cut at the bottom of tower is extracted out through pipeline 34.
The following examples will be further described method provided by the invention, but not thereby limiting the invention.
In embodiment and comparative example, stock oil used is a kind of VGO, and its main character is as shown in table 1.
In embodiment, the trade names of Hydrobon catalyst are RN-32V, and the trade names of back end hydrogenation catalyst for refining are RLF-10
l, by the Chang Ling catalyst plant production and sales of Sinopec catalyzer branch office.In comparative example, the trade names of Hydrobon catalyst used are RN-32V, and the trade names RHC-3 of hydrocracking catalyst used, by the Chang Ling catalyst plant production and sales of Sinopec catalyzer branch office.
In embodiment 1, the preparation process of hydrocracking catalyst A is as follows:
Get C powder and (take from Chang Ling catalyst plant, for a kind of pseudo-boehmite, relative crystallinity 93.1%, 53 microns of grain sizes) 90.2g, aluminum silicon powder (is taken from Chang Ling catalyst plant, silica content 41.3 % by weight) 98.1g, beta80(takes from Chang Ling catalyst plant, silica/alumina 37.6, sodium oxide 0.011 % by weight) 5.6g, several powder are merged, mix, obtain dry powder.Concentrated nitric acid (analytical pure) 5.25mL is added in deionized water 145.5mL, obtain acid solution.By acid solution and dry powder blend, and stir, obtain the raw mixture for extruding, it is 65 ℃ that the temperature of described deionized water makes the temperature of the raw mixture that obtains.The mixture that is 65 ℃ by the temperature obtaining is sent in banded extruder, and mixture is extruded into the trilobal bar that circumscribed circle diameter is 1.6mm, and the temperature of extrudate in the exit of forcing machine is 88 ℃.Extrudate is dried 2.5 hours at 135 ℃, and then, under air atmosphere, under 580 ℃ of conditions, roasting is 4 hours, obtains complex carrier A1 after cooling.The most probable aperture of this complex carrier is that 7.8nm, aperture concentration degree are 16.6.Adopt BET method or mercury penetration method to measure the pore structure of carrier, obtain specific pore volume and amass to the differential in aperture (dV/dr) distribution curve with aperture.
According to tungsten oxide content in catalyzer be 27%, nickel oxide content is 2.5% configuration nickelous nitrate (analytical pure, the sharp chemical reagent factory of Beijing benefit) and ammonium metawolframate (industrial goods, from Chang Ling catalyst plant) hybrid infusion solution, after the saturation method dipping of hole, at 130 ℃, dry 2 hours, thereafter roasting 1.5 hours at 410 ℃, obtains hydrocracking catalyst A.
In embodiment 2, the preparation process of hydrocracking catalyst B is as follows:
Get CL powder 91.5g, aluminum silicon powder SIRAL 20 powder (are purchased the company from sasol, contents on dry basis is 74.5%, for the mixture of the hydrate of aluminum oxide and the hydrate of silicon oxide, in oxide compound, silica content is 20 % by weight, alumina content is 80 % by weight, and average particulate diameter is 53nm) 46.7g, Beta molecular sieve (silica alumina ratio is 60) 1.2g, add sesbania powder 4g and be dry mixed evenly, to obtain dry powder.The concentrated nitric acid of 3.5mL is added in the beaker that is contained with 95mL deionized water, mix, to obtain acid solution.By acid solution and dry powder blend, and stir, obtain the raw mixture for extruding.The mixture obtaining is sent in banded extruder, be extruded into circumscribed circle diameter and be the butterfly bar of 1.4 millimeters, the extrudate temperature in the exit of described forcing machine is 64 ℃.Extrudate is dried to 5 hours at 120 ℃.Then, under air atmosphere, at the temperature of 560 ℃, roasting 3 hours, is cooled to the complex carrier B1 obtaining after room temperature.The most probable aperture of this complex carrier is that 9.1nm, aperture concentration degree are 28.1, and crushing strength is 24.5N/mm.
Ammonium metawolframate (being purchased from Chang Ling catalyst plant) and nickelous nitrate (being purchased from the sharp chemical reagent factory of Beijing benefit) are dissolved in the water, be mixed with steeping fluid, with this steeping fluid, according to hole saturation method, flood complex carrier B1, and the carrier after dipping is dried to 2 hours at 120 ℃ in air atmosphere, then roasting 5 hours in air atmosphere at 350 ℃, thus make hydrocracking catalyst B; The total amount of this catalyzer of take is benchmark, in oxide compound, and WO
3be respectively 27.0 % by weight and 2.6 % by weight with NiO content.
Embodiment 1
Stock oil enters hydrofining reactor after mixing with hydrogen, contact and react with Hydrobon catalyst, the reaction effluent of hydrofining reactor enters hydrocracking reactor, contact with hydrocracking catalyst and carry out hydrocracking reaction, the reaction effluent of hydrocracking reactor removes H through high-pressure stripper
2after S, enter rear refining reaction device, contact and react rear refining reaction with back end hydrogenation catalyst for refining, rear refining reaction device effluent, after separated and fractionation, obtains hydrogen-rich gas, naphtha fraction, intermediate oil and tail oil cut.Concrete reaction conditions is: hydrogen dividing potential drop 13.0MPa(reactor inlet stagnation pressure 14.0MPa), 380 ℃ of hydrofining reactor temperature of reaction, volume space velocity be 1.3h respectively
-1, 382 ℃ of hydrocracking reactor temperature of reaction, volume space velocity 1.5h
-1, 220 ℃ of rear refining reaction device temperature of reaction, volume space velocity 1.5h
-1, high pressure gas stripper pressure 13.5MPa, the temperature of reaction of rear refining reaction device is lower 162 ℃ than the temperature of reaction of hydrocracking reactor.
Acquired results is as shown in table 2, and in liquid product 100%, product naphtha fraction, kerosene(oil)fraction, diesel oil distillate, tail oil cut yield are respectively 23.48%, 14.11%, 32.41% and 30.00%.Wherein, the viscosity index of tail oil cut is 105, condensation point is greater than 300min for-16 ℃, rotary oxygen bomb, and its character meets the index request of II class+lubricant base; And sulphur content of diesel fraction is only for being less than 5 μ g/g, its condensation point is-30 ℃, is the clean low-coagulation diesel oil of high-quality.
Stock oil enters hydrofining reactor after mixing with hydrogen, contact and react with Hydrobon catalyst, the reaction effluent of hydrofining reactor enters hydrocracking reactor, contact with hydrocracking catalyst and carry out hydrocracking reaction, the reaction effluent of hydrocracking reactor removes H through high-pressure stripper
2after S, enter rear refining reaction device, contact and react rear refining reaction with back end hydrogenation catalyst for refining, rear refining reaction device effluent, after separated and fractionation, obtains hydrogen-rich gas, naphtha fraction, intermediate oil and tail oil cut.Concrete reaction conditions is: hydrogen dividing potential drop 14.5MPa(reactor inlet stagnation pressure 15.5MPa), 375 ℃ of hydrofining reactor temperature of reaction, volume space velocity be 1.3h respectively
-1, 392 ℃ of hydrocracking reactor temperature of reaction, volume space velocity 1.6h
-1, 220 ℃ of rear refining reaction device temperature of reaction, volume space velocity 1.3h
-1, high pressure gas stripper pressure 15.0MPa, the temperature of reaction of rear refining reaction device is lower 172 ℃ than the temperature of reaction of hydrocracking reactor.
Acquired results is as shown in table 2, and in liquid product 100%, product naphtha fraction, kerosene(oil)fraction, diesel oil distillate, tail oil cut yield are respectively 36.75%, 19.64%, 28.61% and 15.00%.Wherein, the viscosity index of tail oil cut is 103, condensation point is greater than 300min for-38 ℃, rotary oxygen bomb, and its character meets the index request of II class+lubricant base; And sulphur content of diesel fraction is only for being less than 5 μ g/g, its condensation point is-49 ℃, is the clean low-coagulation diesel oil of high-quality.
Comparative example
Adopt conventional hydrocracking process, stock oil enters hydrofining reactor and hydrocracking reactor successively after mixing with hydrogen, the reaction effluent of hydrocracking reactor obtains hydrogen-rich gas, naphtha fraction, kerosene(oil)fraction, diesel oil distillate and tail oil cut after separated and fractionation.Hydrofining reactor filling Hydrobon catalyst RN-32V, hydrocracking reactor filling hydrocracking catalyst RHC-3, reaction conditions is: hydrogen dividing potential drop 13.0MPa, 373 ℃ of hydrofining reactor medial temperatures, volume space velocity is 1.1h
-1, 380 ℃ of hydrocracking reactor medial temperatures, volume space velocity is 1.7h
-1.
Acquired results is as shown in table 4, and in liquid product 100%, product naphtha fraction, kerosene(oil)fraction, diesel oil distillate and tail oil cut yield are respectively 30.76%, 14.64%, 30.48% and 24.12%.Adopt the conventional method for hydrogen cracking of comparative example, although the hydrocracking tail oil obtaining has higher viscosity index, condensation point higher (32 ℃), oxidation stability is poor, needs further pour point depression, post-refining could meet the requirement of lubricant base.
Table 1 stock oil character
| Stock oil numbering | A |
| Density (20 ℃)/(g/cm 3) | 0.9008 |
| S content/% | 0.92 |
| N content/(μ g/g) | 1600 |
| Condensation point/℃ | 38 |
| Refractive index/n D 70 | 1.4812 |
| Boiling range (D-1160)/℃ | |
| Initial boiling point | 246 |
| 10% | 379 |
| 50% | 439 |
| 90% | 505 |
| Final boiling point | 522 |
Table 2
| Product | Petroleum naphtha | Kerosene | Diesel oil | Tail oil |
| Boiling range scope/℃ | <175 | 175-230 | 230-370 | >370 |
| Liquid product mass yield/% | 23.48 | 14.11 | 32.41 | 30.00 |
| Density (20 ℃)/(g/cm 3) | 0.7128 | 0.7822 | 0.8356 | 0.8589 |
| Total sulfur/(μ g/g) | <1 | <5 | <5 | <5 |
| Total nitrogen/(μ g/g) | <0.5 | <0.5 | <0.5 | <0.5 |
| Smoke point/mm | / | >25 | / | / |
| Cetane value | / | / | >65 | / |
| Condensation point/(℃) | / | / | -30 | -16 |
| Viscosity index | / | / | / | 105 |
| Rotary oxygen bomb/min | >300 |
Table 3
| Product | Petroleum naphtha | Kerosene | Diesel oil | Tail oil |
| Boiling range scope/℃ | <175 | 175-230 | 230-370 | >370 |
| Liquid product mass yield/% | 36.75 | 19.64 | 28.61 | 15.00 |
| Density (20 ℃)/(g/cm 3) | 0.7113 | 0.7812 | 0.8327 | 0.8612 |
| Total sulfur/(μ g/g) | <1 | <5 | <5 | <5 |
| Total nitrogen/(μ g/g) | <0.5 | <0.5 | <0.5 | <0.5 |
| Smoke point/mm | / | >25 | / | / |
| Cetane value | / | / | >65 | / |
| Condensation point/(℃) | / | / | -49 | -38 |
| Viscosity index | / | / | / | 103 |
| Rotary oxygen bomb/min | >300 |
Table 4
| Product | Petroleum naphtha | Kerosene | Diesel oil | Tail oil |
| Boiling range scope/℃ | <175 | 175-230 | 230-370 | >370 |
| Liquid product mass yield/% | 30.76 | 14.64 | 30.48 | 24.12 |
| Density (20 ℃)/(g/cm 3) | 0.7116 | 0.7860 | 0.8266 | 0.8366 |
| Total sulfur/(μ g/g) | <1 | <10 | <10 | <10 |
| Total nitrogen/(μ g/g) | <0.5 | <1 | <1 | <1 |
| Arene underwater content/% | >45 | / | / | / |
| Smoke point/mm | / | >25 | / | / |
| Cetane value | / | / | >65 | / |
| Condensation point/(℃) | / | / | -10 | 32 |
| Viscosity index | / | / | / | 125 |
| Rotary oxygen bomb/min | / | / | / | <200 |
Claims (16)
1. a method of hydrotreating for the low Solidification Point Lube Base Oils of direct production,
(1) stock oil enters hydrofining reactor after mixing with hydrogen, and contact and react with Hydrobon catalyst,
(2) reaction effluent of hydrofining reactor enters hydrocracking reactor, and contact and react with hydrocracking catalyst,
(3) reaction effluent of hydrocracking reactor removes H through high-pressure stripper
2after S, enter rear refining reaction device, contact and react with back end hydrogenation catalyst for refining, described back end hydrogenation catalyst for refining is the loaded catalyst that contains precious metal, and the temperature of reaction of rear refining reaction device is lower 50～200 ℃ than the temperature of reaction of hydrocracking reactor,
(4) after, refining reaction device effluent, after separated and fractionation, obtains hydrogen-rich gas, naphtha fraction, intermediate oil and tail oil cut.
2. in accordance with the method for claim 1, it is characterized in that, the boiling range scope of described stock oil is 300～650 ℃.
3. in accordance with the method for claim 1, it is characterized in that, described stock oil is straight run vacuum gas oil and/or wax tailings, and sulphur content is not more than 50000 μ g/g, and nitrogen content is not more than 5000 μ g/g.
4. in accordance with the method for claim 1, it is characterized in that, the reaction conditions of hydrofining reactor is: 300～450 ℃ of temperature of reaction, and reaction pressure 3.0～20.0MPa, hydrogen to oil volume ratio 300～2000, volume space velocity is 0.1～5.0h
-1;
The reaction conditions of hydrocracking reactor is: temperature of reaction is 300～450 ℃, reaction pressure 3.0～25.0MPa, and hydrogen to oil volume ratio 300～2000, volume space velocity is 0.5～8.0h
-1;
The reaction conditions of rear refining reaction device is: temperature of reaction is 120～300 ℃, and reaction pressure is 3.0～25.0MPa, hydrogen to oil volume ratio 300～2000, and volume space velocity is 0.3～8.0h
-1;
The operational condition of high pressure gas stripper is 3.0～20.0MPa.
5. in accordance with the method for claim 1, it is characterized in that, described Hydrobon catalyst is to load on amorphous alumina or/and the loaded catalyst of the group vib base metal on sial or VIII family base metal or its combination.
6. in accordance with the method for claim 1, it is characterized in that, the carrier of described back end hydrogenation catalyst for refining is heat-resistant inorganic oxide, load hydrogenation activity component, described hydrogenation activity component concentration, in oxide compound, be 0.01～15 heavy %, be selected from least one platinum, palladium precious metal or itself and the group that formed by molybdenum, nickel, vanadium, cobalt, tungsten in the mixture of one or more metals.
7. in accordance with the method for claim 6, it is characterized in that, described hydrogenation active metals component is selected from nickel, platinum and/or the metallic palladium component of group VIII, and in metal and take catalyzer as benchmark, the content of described group VIII metal is 0.1～7 % by weight.
8. according to the method described in claim 7 or 6, it is characterized in that, in described hydrogenation active metals component, contain platinum and palladium, wherein Pd/(Pt+Pd) weight ratio be 0.3～1.0.
9. in accordance with the method for claim 1, it is characterized in that, described hydrocracking catalyst contains complex carrier and loads on group vib metal and the group VIII metal on this complex carrier, in oxide compound, the total amount of this catalyzer of take is benchmark, and the content of described group vib metal is 15～35 % by weight, and the content of described group VIII metal is 2～8 % by weight, the content of described complex carrier is 57～86 % by weight, and wherein complex carrier is comprised of molecular sieve and amorphous composite oxides.
10. in accordance with the method for claim 9, it is characterized in that, in described complex carrier, molecular sieve is beta-molecular sieve, and described amorphous composite oxides are silicon oxide, aluminum oxide, titanium oxide, zirconium white is independent or their arbitrary combination.
11. in accordance with the method for claim 10, it is characterized in that, described complex carrier is comprised of aluminum oxide, silica-alumina and beta-molecular sieve, take complex carrier as benchmark, aluminum oxide 25～80 % by weight, silica-alumina 15～70 % by weight, beta-molecular sieve 0.5～15 % by weight.
12. in accordance with the method for claim 9, it is characterized in that, the most probable aperture of the complex carrier of described hydrocracking catalyst is 3～20nm, the aperture concentration degree of carrier is 15～42, described most probable aperture is to adopt BET method to measure, described aperture concentration degree refers to and adopts in dV/dr that BET method the measures distribution curve with varying aperture, the ratio of the height at peak and the halfwidth at this peak, and dV/dr represents that specific pore volume amasss the differential to aperture.
13. in accordance with the method for claim 9, it is characterized in that, the most probable aperture of the complex carrier of described hydrocracking catalyst is 5～15nm, and the aperture concentration degree of carrier is 18～40.
14. in accordance with the method for claim 9, it is characterized in that, the average particulate diameter of described amorphous composite oxides is 40～100nm.
15. in accordance with the method for claim 9, it is characterized in that, in described amorphous composite oxides, containing relative crystallinity is more than 80% pseudo-boehmite.
16. in accordance with the method for claim 9, it is characterized in that, also contains phosphorus, fluorine, boron, basic metal or alkaline-earth metal or its combination in described hydrocracking catalyst.
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| CN107345163A (en) * | 2016-05-05 | 2017-11-14 | 中国石油化工股份有限公司 | A kind of production method of lube base oil |
| CN116064115A (en) * | 2021-10-31 | 2023-05-05 | 中国石油化工股份有限公司 | Process method for producing naphthenic rubber filling oil by hydrogenation |
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| CN116064115A (en) * | 2021-10-31 | 2023-05-05 | 中国石油化工股份有限公司 | Process method for producing naphthenic rubber filling oil by hydrogenation |
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